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Department of Chemistry, Faculty of Science, Islamic Azad University, Shahrekord Branch, P.O.Box 166, Shahrekord, Iran
Department of Chemistry, Isfahan University of Technology, Isfahan 8415683111, Iran
Institute of Catalysis and Petrochemistry, CSIC, Marie Curie 2, 28049 Madrid, Spain
a r t i c l e
i n f o
Article history:
Received 4 April 2013
Received in revised form 3 October 2013
Accepted 4 October 2013
Available online xxxx
Keywords:
Biodiesel
Nigella sativa
Surfactant
Acid catalyst
Ionic liquid
a b s t r a c t
Two acidic ionic liquids based on 1-benzyl-1H-imidazole have been synthesized and characterized by FT-IR, 1H
NMR, 13C NMR and CHNS analyses. The ionic liquids have been used for transesterication of Nigella sativa
seed oil as newer sources of oil with methanol. We determined relative fatty acid content, iodine and
saponication values of seed oil and estimated cetane number of produced biodiesel based on the chemical
composition of oil. Also, the effect of reaction temperature, type and amount of catalyst, molar ratio and reaction
time were investigated. The results show that the ILH2 ionic liquid has the higher catalytic activity under the
optimized reaction conditions. Thus, this ionic liquid is able to catalyze the transesterication of N. sativa seed
oil to its methyl esters in 6 h with yields of more than 93%. The catalytic activity of ILH2 for the transesterication
of other vegetable oils and alcohols has also been studied.
2013 Elsevier B.V. All rights reserved.
1. Introduction
Biodiesel has gained considerable attention as an alternative fuel
during the past decade due to environmental problems and depletion
of fossil fuels. Indeed, numerous studies have shown the benets of
these alternative fuels [13].
Biodiesel is now mainly produced by transesterication of edible oils
such as canola, palm, safower, soybean and sunower with shortchain alcohols (methanol or ethanol) in the presence of various
catalysts. However, the consumption of edible oils for biodiesel
production has led to food versus fuel problem. Moreover, edible oils'
feedstock costs are far expensive to be used as fuel because 70%80%
of the total cost of biodiesel production is from the raw materials.
Implementation of the biodiesel industry must have a plentiful supply
of raw materials. Therefore, production of biodiesel will only be possible
by using from non-edible oils in an effective way to overcome both
economic and ethical problems [38].
To date, more than 350 oil-bearing crops have been discovered but
the potential of converting these non-edible oils into biodiesel must
be well examined. For example, cetan number (CN), which is a measure
of the ignition quality of diesel fuel during combustion ignition,
provides information about the ignition delay (ID) time of a diesel fuel
upon injection into the combustion chamber. This is one of the most
important parameters considered during the selection of methyl esters
for use as biodiesel [1,3,7].
Corresponding author. Tel.: +98 3813361041; fax: +98 3813361043.
E-mail address: behzad@ch.iut.ac.ir (B. Aghabarari).
0378-3820/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.fuproc.2013.10.003
Nigella sativa with oil content greater than 35%, commonly known as
black seed, belongs to the botanical family of Ranunculaceae. It is native
to Southwest Asia, but it is cultivated in different parts of the world
including Southern Europe, Northern Africa and Asia Minor. It has
been used in many Middle Eastern countries as a natural remedy for
2000 years ago but the use of N. sativa seed oil in large doses and
prolonged use might be harmful due to the presence of some toxic
components such as glucoside in its oil [913]. However, the production
of biodiesel by using N. sativa seed oil as new feedstock can be interesting.
Transesterication reactions can be alkali-catalyzed, acid-catalyzed
or enzyme-catalyzed. The feedstock often contains large amounts of
free fatty acids which would remarkably decrease the effect of base
catalysts. In the presence of basic catalysts, the free fatty acid content
of the oil is saponied by homogeneous alkali catalysts, leading to
depletion of the catalysts as well as to increase purication costs.
Purication of biodiesel and glycerol is easier when enzymes are used
as catalysts but it is not appropriate for industrial scale because enzymes
have high cost and unstable activities [2,14,15]. These problems can be
avoided by the use of homogenous or heterogeneous acid catalysts.
The use of solid acid catalysts eliminates many of the technological
and environmental problems versus homogeneous acid catalysts,
although the process is much slower due to the fact that three phases
are present in the reaction mixture, thus leading to a lower diffusion
coefcient for the heavier molecules to the surface of the solid catalysts.
Several researchers have investigated the use of co-solvents such as
dimethyl ether (DME), tetrahydrofuran (THF), dimethyl sulfoxide
(DMSO) and n-hexane [1519] and phase-transfer catalysts [2023]
to overcome this problem. Gang et al. [20] used both Brnsted and
297
period of 60 min, and then the mixture was reuxed for 24 h. The
solution was cooled to room temperature and about 50 mL of water
was added. The aqueous layer was removed and extracted three times
with dichloromethane. The combined organic layers were added to
the THF solution, then dried over anhydrous sodium sulfate and the
solvent was removed under vacuum.
FT-IR (KBr, cm1): 3441, 3127, 3041, 2975, 1610, 1556, 1498, 1456,
1425, 1374, 757, and 698.
1
H NMR (400 MHz, DMSO-d6) (ppm): 7.81 (s, 1H, NCHN), 7.42
6.91 (m, 7H, ImH and ArH), and 5.49 (s, 2H, NCH2), Anal. calcd for
C10H10N2 (M.W = 158.20): C, 75.92; H, 6.37; N, 17.71; found: C, 75.61;
H, 6.33; and N, 17.54%.
2.2.2. Synthesis of 1-benzyl-3-butyl-1H-imidazolium bromide (ILB1)
1-Benzylimidazole (2.37 g, 15 mmol), was dissolved in 60 mL
acetonitrile in a three-neck round bottom ask and 2.06 g (15 mmol) of
1-bromobutane was added dropwise and the mixture was reuxed for
72 h. After cooling and ltration, the resulting IL was recrystallized twice
in ethyl acetate (100 mL) and then dried under vacuum at 70 C for 12 h.
FT-IR (KBr, cm1): 3454, 3120, 3033, 2918, 2850, 1616, 1558, 1457,
1425, 1376, 1192, 1011, 753, 703, and 452.
1
H NMR (400MHz, DMSO-d6) (ppm): 8.81 (s, 1H, NCHN), 7.55
7.28 (m, 7H, BImH and ArH), 5.54 (s, 2H, NCH2), 4.50 (t, 2H, NCH2),
1.91 (pent, 2H, NCH2*CH2), 1.30 (pent, 2H, NCH2CH2*CH2),
and 0.83 (t, 3H,CH3), Anal. calcd. for C14H19BrN2 (M.W = 295.22):
C, 56.96; H, 6.49; and N, 9.49; found: C, 56.31; H, 6.38; and N, 9.61.
2.2.3. Synthesis of 3-butyl-6-sulfo-1-(4-sulfobenzyl)-1H-imidazolium
hydrogen sulfate (ILB2)
To the 10 g concentrated H2SO4 (98%) that previously cooled in an
ice bath, ILB1 (2.95 g, 10 mmol) was added slowly and mixed at this
temperature for 8 h. After this time, the mixture was stirred for 24 h at
80 C to form ILB2. Upon completion, the reaction mixture was cooled
in an ice bath and then the solid product separated and dried under
high vacuum at 70 C for 4 h.
FT-IR (KBr, cm1): 3455, 3125, 3034, 2921, 2850, 1615, 1560, 1489,
1465, 1428, 1377, 1342, 1221, 1192, 1061, 1009, 855, 765, 719, 700, 619,
588, and 423.
1
H NMR (400 MHz, DMSO-d6) (ppm):8.78 (s, 1H, NCHN), 7.66
7.35 (m, 7H, BImH and ArH), 5.75 (s, 2H, CH2), 4.54 (t, 2H, NCH2),
1.90 (pent, 2H, NCH2*CH2), 1.21 (m, 26H, CH2(13)), 0.86 (t, 3H,CH3),
13
C NMR (400 MHz, DMSO-d6) (ppm): 143.18, 138.15, 136.25,
129.91, 128.86, 126.73, 121.62, 51.08, 47.75, 32.63, 31.94, 29.58, 29.41,
29.34, 29.18, 28.93, 28.57, 26.25, 22.54, and 14.37, Anal. calcd. for
C14H20N2O7S2 (M.W = 392.45): C 42.85; H 5.14; N 7.14; and S 16.34
found: C 42.91; H 5.08; N 7.12; and S 16.19.
2.2.4. Synthesis of 1-benzyl-3-hexadecyl-1H-imidazolium bromide (ILH1)
Compound ILH1 was prepared following the same procedure as for
ILB1 except that we used 4.58 g (15 mmol) 1-bromohexadecane for
synthesis of ILH1.
FT-IR (KBr, cm1): 3454, 3121, 3038, 2919, 2850, 1616, 1559, 1458,
1428, 1376, 1194, 1015, 763, 703, and 454.
298
1
H NMR (400 MHz, DMSO-d6) (ppm): 8.81 (s, 1H, NCHN), 7.55
7.28 (m, 7H, BImH and ArH), 5.74 (s, 2H, NCH2), 4.50 (t, 2H, NCH2),
1.91 (pent, 2H, NCH2*CH2), 1.21 (m, 26H, CH2(13)), and 0.83 (t, 3H,
CH3), Anal. calcd. for C26H43BrN2 (M.W = 463.54): C, 67.37; H, 9.35;
and N, 6.04; found: C, 67.14; H, 9.39; and N, 6.11.
Table 1
Chemical composition of Nigella sativa seed oil.
Fatty acid
MW(gmol1)
Composition (wt.%)
256.43
284.48
282.47
280.45
278.44
312.53
310.51
340.58
18.8
4.6
23.1
50.3
0.2
0.6
0.2
2.2
In this study, the cetane numbers of the biodiesel produced from the
N. sativa seed oil are estimated by using the last two equations (Table 2).
According to the physicochemical characterization and the estimated
cetane numbers, the biodiesel produced from the N. sativa seed oil can
meet the USA biodiesel standard and can be developed as potential
energy plant.
4.2. The effect of temperature and catalyst
N. sativa seed oil was transesteried with methanol in the
temperature range of 4575 C, in steps of 15 C, for 5 h (Table 3).
The molar ratio of methanol (MEA) to N. sativa seed oil (NSO) was
6:1 and the ionic liquids (5%, based on mmol of oil) was used as
299
Table 4
Calculation and comparison of H0 values of different ionic liquids in CH2Cl2.
Entry
Fuel properties
Unit
Calculated value
Entry
Ionic liquid
Amaxa
[I] (%)
[IH+] (%)
H0
1
2
3
4
5
(g of I2/100 g of oil)
(mg of KOH/g of oil)
112.5
201.8
124.5
48.0
50.0
1
2
3
Blank
ILB2
ILH2
2.28
0.99
0.93
100
43.4
40.8
0
56.6
59.2
0.87
0.83
(min)
(min)
h
i
:
H0 pKIaq log I= IH
From the data presented in Table 4, the acidity of ILB2 (H0 = 0.87) is
a little higher than that of ILH2 (H0 = 0.84). According to the elemental
analysis and Hammett acidity function results, there isn't heavy
difference between acidity of ILB2 and ILH2. However the higher
catalytic activity of ILH2, than that of ILB2, can be related to its surfactant
properties that can increase its interaction with hydrophobic reagents.
The long carbon chains connected to the imidazolium moiety of catalyst
increase the interaction between the hydrophobic feedstock and its
Brnsted acidic sites. Gang et al. [20] used surfactant-combined
catalysts dodecylbenzenesulfonic acid and copper dodecylbenzene
Table 3
Effect of reaction temperature and different ionic liquids on the transesterication of
Nigella sativa seed oil with methanol.
Entry
Catalyst
Temperature (C)
Conversion (wt.%)
1
2
3
4
5
6
7
8
9
H2SO4
45
60
75
45
60
75
45
60
75
23.1
34.7
40.3
51.6
64.8
65.5
64.5
75.3
73.0
ILB2
ILH2
Reaction conditions: amount of catalyst = 5% (based on the mmol of oil), MEA/NSO (molar
ratio) = 6, reaction time = 5 h.
100
95
90
Conversion (%)
85
80
75
70
65
60
55
50
0
12
15
300
100
Table 5
Effect of amount of catalyst on the tranesterication of Nigella sativa seed oil with
methanol.
90
blank
0
1
48.9
2.5
77.4
5
82.6
7.5
89.0
10
86.6
Conversion (%)
80
Entry
70
60
50
40
30
20
10
The effect of the reaction time on the transesterication of N. sativa
seed oil was determined using 7.5% of ILH2, a MEA:NSO molar ratio of
9 and a temperature of 60 C. Fig. 2 shows that the conversion increased
from 40.5% to about 93.2% after 6 h, with little change after this time.
This observation remembers that the transesterication of vegetable
oil is a reversible reaction with an equilibrium time of around 6 h,
which was therefore taken as the ideal time for the transesterication
of N. sativa seed oil with methanol.
4.5. Catalyst recyclability
One of the most important factors in designing a new catalyst could
be the reusability of a catalyst. The catalytic stability of ILH2 was
investigated by performing seven runs under the optimized reaction
conditions determined above (Fig. 3). The catalyst was separated,
washed and dried as described in the Experimental section after each
run. It was revealed that the activity of catalyst remained almost steady
after seven runs and decrease in the conversion was negligible (rst
run = 93.2%, seventh run = 89.4%). In addition to high catalytic activity,
this result indicates that the ILH2 ionic liquid is recyclable and has
desirable properties for the transesterication reaction of N. sativa
seed oil with methanol.
4.6. The effect of the type of alcohol or fatty acid
The result listed in Table 6 exhibited the type of alcohol or fatty acid
that had inuence on the conversion of transesterication over ILH2
catalyst at optimum reaction condition. To investigate the effect of the
length of the alcohol alkyl chain, we studied the transesterication of
N. sativa seed oil with methanol, ethanol and n-butanol under the
optimized reaction conditions. Two main alcohol properties, namely
the miscibility with triglyceride molecule and steric hindrance, have a
major inuence on the conversion of transesterication of N. sativa
seed oil. Clearly, alcohols with longer alkyl chain have higher miscibility
100
Conversion (%)
90
80
0
1
Run
Fig. 3. Catalyst recycling of transesterication of Nigella sativa seed oil with methanol using
ILH2.
with oil but less nucleophilicity property for the attack to the activated
carbonyl group of triglyceride molecule. The result showed that the
use of ethanol instead of methanol had no major effect on the yield of
the reaction, although a further increase in the number of carbon
atoms in the alkyl chain resulted in a decrease in the conversion from
93.2% for methanol to 88.5% for n-butanol, probably the steric hindrance
of alcohol has more inuence on the conversion of reaction.
We also studied the catalytic activity of ILH2 for the transesterication
of other vegetable oils and found that the degree of saturation (DS)
of the fatty acid had an inverse effect on the conversion. Thus, the
transesterication yields for canola oil (DS = 7.7%), N. sativa seed oil
(DS = 25.9%), and palm oil (DS = 46.7%) under the optimized reaction
conditions were 97.7, 93.2% and 85.6%, respectively. The result show
that the oils with a higher degree of saturation are likely to be more
packed and therefore less likely to approach the active site of the catalyst,
Furthermore, methanol would not penetrate well into such a packed
structure.
5. Conclusion
In this study, we have synthesized and characterized two acidic ionic
liquids (ILB2 and ILH2). The experimental results have shown ILH2 to
be more active than ILB2 in the transesterication of N. sativa seed
oil with methanol. Also based on the seed oil properties and the
estimated cetane number, the N. sativa seed oil can be developed as a
biodiesel feed stock. A conversion of more than 93% has been obtained
for the transesterication of this oil with methanol upon varying several
reaction parameters, including temperature, molar ratio, amount of
catalyst and reaction time. Furthermore, satisfactory yields (85.697.7%)
have been obtained for the transesterication of several different alcohols
Table 6
Effect of type of alcohol and oil on the tansesterication reaction.
70
Entry
Vegetable oil
1
2
3
4
5
6
7
8
Canola
Safower
Sunower
Soybean
Nigella sativa
Nigella sativa
Nigella sativa
Palm
60
50
40
30
30
60
90 120 150 180 210 240 270 300 330 360 390
Unsaturated
7.7
10.7
11.4
14.1
25.9
25.9
25.9
46.7
92.3
89.3
88.6
85.9
74.1
74.1
74.1
53.3
Alcohol
Conversion (wt.%)
Methanol
Methanol
Methanol
Methanol
Methanol
Ethanol
n-Butanol
Methanol
97.7
96.8
97.0
96.2
93.2
93.3
88.5
85.6
Reaction conditions: catalyst = ILH2, catalyst weight = 7.5% (based on the mmol of oil),
alcohol/NSO (molar ratio) = 9, reaction temperature = 60 C, reaction time = 6 h.
301
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